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1. 发明授权

US4197123A Process for the production of masked positive color images by the silver dye bleach process 失效
标题翻译：通过银染料漂白工艺生产掩蔽的正彩色图像的工艺
公开(公告)号：US4197123A
公开(公告)日：1980-04-08
申请号：US924476
申请日：1978-07-13
申请人： Alfred Oetiker , Christoph Chylewski , Max Marthaler
发明人： Alfred Oetiker , Christoph Chylewski , Max Marthaler
IPC分类号： G03C7/02 , G03C7/28 , G03F1/00 , G03F1/02 , G03C7/04 , G03C7/16
CPC分类号： G03C7/28
摘要： The present invention provides a new process for the production of masked subtractive positive color images by the silver dye bleach process, which comprises the steps of exposure, silver developing, dye-bleaching, silver-bleaching and fixing. The photographic material used contains, in at least two layers, one image-wise bleachable dye per layer, the absorption maximum of the dye corresponding in each case to one of the three primary colors red, green and blue and a silver halide emulsion layer sensitive in a specific spectral region being allocated to each dye, wherein this material (a) in at least one layer contains a dye, the undesired secondary color density of which is to be compensated, and a silver halide emulsion containing silver iodide is allocated to this dye, in the same layer and/or an adjacent layer, (b) in at least one further layer contains at least one further dye, the main color density of which corresponds to a secondary color density, which is to be compensated, of the first dye, and also a silver halide emulsion free from iodide ions, (c) contains a further layer which is adjacent to layer (b) and contains colloidal nuclei which are able, under reducing conditions, to deposit metallic silver from soluble silver complexes, and also contains an insensitive iodide-free silver halide emulsion which is not spectrally sensitized, and optionally a stabilizer, and (d) containing a separating layer, which does not contain any of the dyes of the layer or layers (a), between the layer or layers (a) and the layer (c). The silver developing bath with which the material is treated contains ligands which form water-soluble and diffusible silver complexes with silver.
摘要翻译：本发明提供了一种用于通过银染料漂白方法生产掩蔽的减去正彩色图像的新方法，其包括曝光，银显影，染料漂白，银漂白和定影的步骤。使用的照相材料在至少两层中每层含有一个成像漂白染料，染料在每种情况下的吸收最大值分别为三原色之一，红色，绿色和蓝色，卤化银乳剂层敏感在分配给每种染料的特定光谱区域中，其中至少一层中的该材料（a）含有染料，其不希望的二次色密度被补偿，并且将含有碘化银的卤化银乳剂分配给该染料在同一层和/或相邻层中的染料，（b）在至少一个另外的层中含有至少一种另外的染料，其主要颜色密度对应于要补偿的第二颜色密度第一染料，以及不含碘离子的卤化银乳剂，（c）含有与层（b）相邻的另一层，并含有胶体核，其能够在还原条件下从solubl沉积金属银 e银络合物，并且还含有不受光谱敏化的不含碘化物的卤化银乳剂，以及任选的稳定剂，和（d）含有不含任何层或层的染料的分离层（a ），层或层（a）和层（c）之间。处理材料的银显影槽含有与银形成水溶性和可扩散的银络合物的配体。

2. 发明授权

US3963492A Method for processing silver dye bleach materials 失效
标题翻译：银染料漂白剂处理方法
公开(公告)号：US3963492A
公开(公告)日：1976-06-15
申请号：US510967
申请日：1974-10-01
申请人： Max Marthaler , Matthias Schellenberg , Herbert Mollet , Christoph Chylewski
发明人： Max Marthaler , Matthias Schellenberg , Herbert Mollet , Christoph Chylewski
IPC分类号： G03C7/02 , G03C5/44 , G03C7/28 , G03C7/00
CPC分类号： G03C7/28 , G03C5/44
摘要： The present invention relates to a simplified method for processing silver dye bleach material by (1) silver developing, (2) dye and silver bleaching (3) silver fixing and (4) soaking. The sequence (1), (2), (3), (4) is followed and the bleaching bath (2) contains (a) a strong acid, (b) a water-soluble iodide, (c) a water-soluble oxidizing agent (d) an antioxidant and (e) a dye bleach catalyst.
摘要翻译：本发明涉及通过（1）银显影，（2）染料和银漂白（3）银固色和（4）浸泡来处理银染料漂白材料的简化方法。遵循序列（1），（2），（3），（4），漂白浴（2）含有（a）强酸，（b）水溶性碘化物，（c）水溶性氧化剂（d）抗氧化剂和（e）染料漂白催化剂。

3. 发明授权

US3961957A Dye bleach preparation for the photographic silver dye bleach process 失效
标题翻译：染料漂白剂用于摄影银染料漂白工艺
公开(公告)号：US3961957A
公开(公告)日：1976-06-08
申请号：US468838
申请日：1974-05-10
申请人： Ekkehard Kramp , John Lenoir , Max Marthaler , Robert Schaller
发明人： Ekkehard Kramp , John Lenoir , Max Marthaler , Robert Schaller
IPC分类号： G03C7/02 , G03C5/44 , G03C7/28 , G03C7/00
CPC分类号： G03C5/44
摘要： The invention relates to a dye bleach preparation which contains in addition to an acid, a water-soluble iodide and optionally a dye bleach catalyst at least one bifunctional sulphur compound having a sufficient solubility in the preparation and a low vapor pressure and containing at least one HS-group and at least one oxygen, nitrogen, phosphorus or additional sulphur atom, the sulphur atom of each HS-group being separated from the next oxygen, sulphur, nitrogen and phosphorus atom present in the molecule by at least three carbon atoms.The subject of the present invention is a dye bleach preparation for the photographic silver dye bleach process, which contains an acid, a water-soluble iodide and optionally a dye bleach catalyst. The preparation is characterised in that it contains at least one organic, at least bifunctional sulphur compound of which the solubility is at least 5.times.10.sup.-.sup.4 mol per liter of preparation and of which the vapour pressure in the temperature range of -20.degree.C to +100.degree. C is at most as great as that of water, and which contains at least one HS-- group and at least one oxygen, nitrogen, phosphorus or additional sulphur atom, with the sulphur atom of each HS-- group being separated from the next oxygen, sulphur, nitrogen and phosphorus atom present in the molecule by at least three carbon atoms.The HS-- group can also be separated from the next oxygen, nitrogen, phosphorus or sulphur atom by a ring system, where in every case the shortest link between the two hetero-atoms must comprise at least three carbon atoms.Preferred sulphur compounds correspond to the formulae (1) to (16) which follow: ##EQU1##In these formulae, the symbols in every case have the same meaning, and in particular denote the following:A. an aliphatic, araliphatic or heterocyclic bridge member.A.sub.1. an aliphatic bridge member, an aralkylene radical, an aralkylidene radical or a benzene radical which is bonded, on non-adjacent carbon atoms, to the H-S- and B.sub.1 -groups.B. one of the groups of the formulae ##EQU2## wherein M denotes a cation, X denotes an anion, R.sub.1 and R.sub.2 denote a hydrogen atom, a lower alkyl group, a lower hydroxyalkyl group or the radical of a benzenesulphonic acid and R.sub.3 denotes a lower alkyl group and R.sub.1 and R.sub.2 located on the same nitrogen atom can also form a heterocyclic ring with the latter. B.sub.1. one of the groups ##EQU3## --SO.sub.3 M, --COOH (for R.sub.1 and R.sub.2, see above). B.sub.2. one of the groups --COOH, --SO.sub.3 cation, ##EQU4## --N(CH.sub.3).sub.2, --N(C.sub.2 H.sub.5).sub.2 (for R.sub.1 and R.sub.2, see above).B.sub.3. one of the groups --COOH, --SO.sub.3 cation and ##EQU5## (for R.sub.1 and R.sub.2, see above). B.sub.4. a carboxylic acid amide group (which can optionally carry one or two substituents on the nitrogen atom) or a sulphonic acid group (optionally in the form of a salt).M.sub.1. one of the cations H, Na, K, NH.sub.4, ##EQU6##m, n, p, q, r, s and t denote integers, as follows:1 .ltoreq. m .ltoreq. 4 1 .ltoreq. n .ltoreq. 2 1 .ltoreq. p .ltoreq. 2 2 .ltoreq. q .ltoreq. 12 2 .ltoreq. r .ltoreq. 6 1 .ltoreq. s .ltoreq. 4 1 .ltoreq. t .ltoreq. 2 3 .ltoreq. s + t The following compounds may be mentioned as examples: 3-Mercapto-propionic acid, 3-mercapto-propionic acid amide, 3-mercapto-propionic acid N-(4'-sulpho-phenyl)amide, 3-mercapto-propionic acid N-(3'-sulpho-phenyl)amide, 3-mercapto-propionic acid N,N-di-(.beta. -hydroxyethyl)-amide, the guanidinium salt of 3-mercapto-propanesulphonic acid, 3-mercapto-1-dimethylaminopropane, 3-mercapto-butyric acid, 4-mercapto-butyric acid, 4-mercapto-butyric acid amide, 4-mercapto-butyric acid N-(4'-sulpho-phenyl)-amide, 4-mercapto-butyric acid N-(.beta.-hydroxyethyl)-amide, 4-mercapto-butyric acid N-(6'-sulpho-naphthyl)-amide, 1-mercapto-butane-4-sulphonic acid, 1-mercapto-n-pentane-5-sulphonic acid, 1-mercapto-hexane-6-sulphonic acid, 10-mercapto-decane-1-sulphonic acid, 4-mercapto-1-diethylaminobutane hydrobromide, 4-mercapto-butane-phosphonic acid, 4-mercapto-butanol-(1), 4-mercapto-butyric acid N-(4'-sulphamoyl-phenyl)-amide, 6-mercapto-caproic acid, 5-mercapto-caproic acid, 3-mercapto-valeric acid, 4-mercapto-valeric acid, 5-mercapto-valeric acid, 3-mercapto-2-(mercaptomethyl)-propionic acid, 2-(mercaptomethyl)-succinic acid, 4-mercapto-butyronitrile, 1,3-dimercapto-2-methylpropane, 5-mercaptopentanephosphonic acid, 3-mercaptopropanephosphonic acid monoethyl ester, 3-mercapto-hexane-1,6-dicarboxylic acid, 4-mercaptobutyric acid .beta.-methoxyethyl ester, 4-mercaptobutyric acid .beta.-hydroxyethyl ester, .alpha.-methylmercaptotoluene-4-sulphonic acid, 3- or 4-amino-thio-phenol, 3-mercaptophenyl-N,N,N-trimethylammonium iodide, 4-mercapto-pyridine, 4-mercaptobenzenesulphonic acid, 4-N,N-dimethylamino-1-mercaptobenzene, 5-methyl-4-mercapto-caproic acid, 4,5-dimethyl-4-mercapto-caproic acid and 4,5-dimethyl-5-mercapto-caproic acid.The sulphur compounds to be used according to the invention can also be added to the dye bleach preparation in the form of their salts, especially of the alkali metal salts, or of inorganic or organic ammonium salts.In general it suffices to use 1 to 10 mol per cent of the sulphur compound, relative to the amount of iodide present, and if appropriate solvents, such as dimethylformamide, tetrahydrofurane or benzyl alcohol can also be added to the dye bleach preparation.Examples of suitable acids for the dye bleach baths are sodium bisulphate, sulphamic acid, acetic acid, citric acid, organic sulphonic acid, hydrochloric acid, sulphuric acid or phosphoric acid.The water-soluble iodide can be, for example, potassium iodide, sodium iodide, ammonium iodide or hydriodic acid.The dye bleach catalyst can either be dissolved in the dye bleach preparation or be contained in the photographic material to be bleached and can be, for example, a pyrazine, a quinoxaline or a phenazine.The sulphur compounds can be solid or liquid at room temperature and, as mentioned, their vapour pressure within the temperature range of -20.degree.C to +100.degree.C may only be at most equal to the vapour pressure of water.Alternatively to being in the form of a bath, the dye bleach preparation can, for example, also be a gel-like thickened composition, in the form of a colloidal mass or photographic layer. By using suitable technical measures such as, for example, providing protective layers or encapsulating the active components, the dye bleach preparations can be introduced into a photographic material in such a way that the dye-bleaching action can only come into operation on processing the photographic material. In special cases, mixtures of the iodide and of the sulphur compounds can also be present as such, whilst the acid and dye bleach catalyst are accommodated in another phase (compare, for example, French Pat. Specification 1,504.238).When using the dye bleach preparation according to the invention for bleaching reducible image substances, such as azo dyestuffs, nitro dyestuffs and diazonium salts, in the presence of metallic images, these metallic images can, in a known manner, be the converse of the original (negative) or in the same sense as the original (positive). It is desirable, after developing and before the dye-bleaching, to dissolve out of the material all metal salts, such as silver chloride or silver bromide, which may still be present (that is to say to fix the material), since otherwise the iodide content of the dye bleach bath would rapidly be exhausted and major amounts of sparingly soluble silver iodide would form at the same time. After the dye-bleaching, the silver which remains is removed in a known manner.In addition to the constitutents mentioned, the dye bleach baths can contain customary additives such as complex-forming agents, wetting agents and solvents.The dye bleach baths according to the present invention remain stable for a long period, do not undergo any discolouration, give results of good reproductibility even in continuously operating machines and in addition exhibit very advantageous behaviour with regard to corrosion of the containers and parts of the apparatus with which they come into contact. The sulphur compounds of the indicated composition which are present in the baths do not increase the corrosiveness and in some cases even reduces it. The particularly favourable behaviour of these sulphur compounds with regard to corrosion, even in comparison with such mercapto compounds as, for example, 1-mercapto-2,3-propanediol or 2-mercaptosuccinic acid, which do not have the composition circumscribed at the beginning of this text, can be demonstrated by various methods, for example also by electrochemical and therefore time-saving methods.In the examples which follow, percentages denote percentages by weight.
摘要翻译：本发明涉及一种除了酸，水溶性碘化物和任选的染料漂白催化剂外还含有至少一种具有足够的二官能硫化合物的染料漂白剂

4. 发明授权

US4254215A Process for the prevention of darkening and the formation of a sediment in photographic developer solutions 失效
标题翻译：防止变色和照相显影剂溶液中沉淀物形成的方法
公开(公告)号：US4254215A
公开(公告)日：1981-03-03
申请号：US024287
申请日：1979-03-26
申请人： Ekkehard Kramp , John Lenoir , Max Marthaler
发明人： Ekkehard Kramp , John Lenoir , Max Marthaler
IPC分类号： G03C5/305 , G03C5/30 , G03C5/38
CPC分类号： G03C5/305
摘要： A process is described for the prevention of darkening and the formation of a sediment in photographic developer solutions which contain a silver halide developer, a water-soluble silver halide solvent and organic sulfur compounds. The organic sulfur compounds are a combination of (a) an organic thiol compound or thione compound capable of tautomerism and (b) a Bunte salt which contains groups conferring solubility in water. Developer solutions which contain the indicated combination of sulfur compounds are outstandingly stable.
摘要翻译：描述了一种防止变色和在含有卤化银显影剂，水溶性卤化银溶剂和有机硫化合物的照相显影剂溶液中形成沉淀物的方法。有机硫化合物是（a）能够互变异构化的有机硫醇化合物或硫酮化合物的组合，和（b）包含赋予溶于水的基团的Bunte盐的组合。含有指示的硫化合物组合的显影剂溶液显着稳定。

5. 发明授权

US4141734A Photographic developing process 失效
标题翻译：摄影发展过程
公开(公告)号：US4141734A
公开(公告)日：1979-02-27
申请号：US856389
申请日：1977-12-01
申请人： John Lenoir , Max Marthaler
发明人： John Lenoir , Max Marthaler
IPC分类号： C07D239/46 , C07D307/54 , C07D333/24 , G03C5/305 , G03C5/38 , G03C5/50 , G03C7/00 , G03C5/30
CPC分类号： C07D239/47 , C07C323/00 , C07D307/54 , C07D333/24 , G03C5/305 , G03C5/383 , G03C5/50
摘要： A process for developing photographic silver halide material, which has been exposed image-wise is provided. The aqueous developer preparation used contains a developer compound for the silver halide, a water-soluble solvent for the silver halide and an aliphatic, cycloaliphatic, aromatic or heterocyclic di- or trisulphide. These preparations remain clear over a long period of time during which they do not lose their effectiveness by becoming turbid or by sedimentation of silver. They are of special advantage in continuously operated photographic developing processes.
摘要翻译：提供了已经成像曝光的照相卤化银材料的开发方法。所用的含水显影剂制剂含有用于卤化银的显影剂化合物，卤化银的水溶性溶剂和脂族，脂环族，芳族或杂环二 - 或三硫化物。这些制剂在长时间内保持清晰，在此期间，它们不会因浑浊或沉淀银而失去效力。它们在持续运行的照相显影工艺中具有特别的优点。

6. 发明授权

US4304846A Method for processing silver dye-bleach materials 失效
标题翻译：银染料漂白材料的处理方法
公开(公告)号：US4304846A
公开(公告)日：1981-12-08
申请号：US118245
申请日：1980-02-04
申请人： Max Marthaler , Gerald Jan
发明人： Max Marthaler , Gerald Jan
IPC分类号： G03C7/02 , G03C5/44 , G03C7/28 , G03C7/00
CPC分类号： G03C5/44 , G03C7/28
摘要： A method for processing exposed silver dye-bleach materials using novel preparations for combined dye bleaching and silver bleaching is described. In addition to a strong acid, a water-soluble iodide, a water-soluble oxidizing agent, an antioxidant and, if desired, a bleaching accelerator, these preparations also contain a mixture of 1,4- or 1,2-diazines as bleach catalysts. This mixture consists either of at least two bleach catalysts with redox potentials between +105 mV and -30 mV, the difference between the redox potentials of the catalysts being at least 15 mV, or of at least one bleach catalyst with a redox potential between +60 mV and -30 mV and at least one bleach catalyst with a redox potential between -30 mV and -100 mV, the difference between the redox potentials of the catalysts likewise being at least 15 mV.When exposed dye-bleach materials are processed using these preparations, images with improved color quality are obtained.
摘要翻译：描述了使用用于组合染料漂白和银漂白的新型制剂来处理曝光的银染料漂白材料的方法。除了强酸，水溶性碘化物，水溶性氧化剂，抗氧化剂，如果需要，还有漂白促进剂，这些制剂还含有1,4-或1,2-二嗪作为漂白剂的混合物催化剂。该混合物由至少两种具有+105mV和-30mV之间的氧化还原电位的漂白催化剂组成，催化剂的氧化还原电位之间的差异至少为15mV，或至少一种氧化还原电位在+ 60 mV和-30 mV以及至少一种氧化还原电位在-30 mV和-100 mV之间的漂白催化剂，催化剂的氧化还原电位之间的差异同样至少为15 mV。当使用这些制剂处理曝光的染料漂白材料时，获得具有改善的颜色质量的图像。

7. 发明授权

US4046566A Process for the production of masked positive color images by the silver dye bleach process using silver complex diffusion 失效
标题翻译：通过使用银复合扩散的银染色漂白工艺生产掩蔽的正彩色图像的过程
公开(公告)号：US4046566A
公开(公告)日：1977-09-06
申请号：US625235
申请日：1975-10-23
申请人： Max Marthaler
发明人： Max Marthaler
IPC分类号： G03C7/02 , G03B33/00 , G03C7/28 , G03C7/04 , G03C1/76 , G03C3/00
CPC分类号： G03C7/28
摘要： The present invention relates to a process for the production of masked subtractive positive color images in accordance with the silver dye bleach process. In the material to be processedA. a silver halide emulsion layer consisting at least partially of silver iodide is allocated to the dyestuff, of which the undesired parasitic color density is to be compensated,B. in a further layer, at least one second dyestuff, of which the main color density corresponds to a parasitic color density, requiring compensation, of the first dyestuff, and a silver halide emulsion free from iodide ions, are present,C. a further layer, which is adjacent to that containing the second dyestuff, contains colloidal nuclei which are capable of depositing metallic silver from soluble silver complexes,D. a separating layer is present between the layer containing the nuclei and the dyestuff layer, of which the parasitic color density is to be compensated.The silver developer bath, with which the material is treated contains a ligand, which is able to produce water-soluble silver complexes which are capable of diffusion.

8. 发明授权

US4014698A Method for processing silver dye bleach materials 失效
标题翻译：银染料漂白剂处理方法
公开(公告)号：US4014698A
公开(公告)日：1977-03-29
申请号：US591803
申请日：1975-06-30
申请人： Max Marthaler
发明人： Max Marthaler
IPC分类号： G03C7/02 , G03C5/44 , G03C7/28 , G03C7/00
CPC分类号： G03C7/28 , G03C5/44
摘要： The present invention relates to a new method for processing silver dye bleach material. The process measures of this method, consisting of (1) silver developing, (2) dye bleaching, (3) silver bleaching, (4) silver fixing are carried out in the sequence (1) to (4) with appropriate preparations. The silver bleaching (3) preparation contains (a) a strong acid, (b) a water-soluble iodide, (c) a water-soluble oxidizing agent, (d) a diazine compound and (e) an anti-oxidant. An excellent and rapid bleaching is achieved.
摘要翻译：本发明涉及一种加工银染料漂白材料的新方法。该方法由（1）银显影，（2）染料漂白，（3）银漂白，（4）银固色组成的该方法的工艺步骤按照顺序（1）至（4）进行适当的制备。银漂白（3）制剂含有（a）强酸，（b）水溶性碘化物，（c）水溶性氧化剂，（d）二嗪化合物和（e）抗氧化剂。实现了优异快速的漂白。

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